Pollution characteristics and biodegradation mechanism of petroleum hydrocarbons in gas station groundwater in the Tianjin Plain

doi:10.13745/j.esf.sf.2022.1.41

Abstract

Abstract:

Petroleum hydrocarbon pollution in gas station groundwater is a common phenomenon. This study sought to sample and analyze gas station groundwater under various hydrogeological conditions to determine the pollution characteristics of petroleum hydrocarbon in gas station groundwater and the characteristics of groundwater chemical types. Factor analysis, correlation analysis, and multiple regression analysis were used to reveal the potential biodegradation mechanism of petroleum hydrocarbon in gas station groundwater. According to the results, groundwater chemicals can be mainly divided into four types: Cl-Na, HCO₃-Na, HCO₃-Ca, and SO₄-Na types. The detection rate of petroleum hydrocarbons in the groundwater was 85.71%, and the detection concentration range was 0.02-0.35 mg/L. Factor analysis revealed that the main factors affecting the chemical composition of groundwater were water-rock interaction and biodegradation of petroleum hydrocarbons. The correlation between TPH and groundwater chemical indexes showed that the total petroleum hydrocarbon (TPH) was negatively correlated with K⁺, Na⁺, Cl^-, Mn, Mg²⁺, and $SO 4 2 -$ , but not significantly correlated with pH, $HCO 3 -$ , $NO 3 -$ , $NO 2 -$ , Ca²⁺, and Fe. Halophilic or salt-tolerant microorganisms might also be present in the gas station groundwater environment, which accelerates the TPH biodegradation rate as TPH concentration decreases with increasing salinity. In the microorganism degradation of TPH using electron acceptors ( $SO 4 2 -$ , Mn, $NO 3 -$ , Fe), the contribution percentage of electron acceptors were ranked as iron reduction (64.88%) >manganese reduction (24.86%) >sulfate reduction (5.78%) >nitrate reduction (4.46%). Thus, the biodegradation of petroleum hydrocarbons by Fe-Mg-reducing bacteria in gas station groundwater is the dominant reaction.

Key words: gas station, groundwater, petroleum hydrocarbon, biodegradation

CLC Number:

X523

LIU Xuena, LI Haiming, LI Mengdi, ZHANG Weihua, XIAO Han. Pollution characteristics and biodegradation mechanism of petroleum hydrocarbons in gas station groundwater in the Tianjin Plain[J]. Earth Science Frontiers, 2022, 29(3): 227-238.

Figures/Tables 10

Fig.1 Schematic map showing the location of gas station sampling sites and groundwater flow field in the Tianjin coastal plain area. Adapted from [19].

Fig.2 Spatial distribution of TPH concentrations in the Tianjin coastal plain area

Table 1 Statistics of gas station groundwater hydrochemical indexes for the study area

组分及参数	样本量	极大值	极小值	均值	标准差	变异系数/%
TDS	84	2.30×10⁴	656.00	4 376.54	5 289.01	120.85
K⁺	84	149.00	0.59	24.46	37.78	154.46
Na⁺	84	6.98×10³	50.30	1 184.35	1 568.53	132.44
Ca²⁺	84	929.00	18.20	158.20	141.47	89.42
Mg²⁺	84	939.00	7.24	174.91	188.50	107.77
$HCO 3 -$	84	1.89×10³	87.00	688.45	267.73	38.89
Cl^-	84	1.20×10⁴	35.00	1 930.96	2 988.43	154.76
$SO 4 2 -$	84	1.44×10³	33.00	399.99	337.47	84.37
$CO 3 2 -$	84	ND	ND
$NO 3 -$	84	148.00	ND	9.61	19.74	205.36
$NO 2 -$	84	5.57	ND	0.18	0.61	344.54
Mn	84	8.02	ND	0.70	1.32	187.17
Fe	84	2.54	ND	0.19	0.53	271.73
pH值	84	8.73	6.80	7.43	0.34	4.56

Table 1 Statistics of gas station groundwater hydrochemical indexes for the study area

组分及参数	样本量	极大值	极小值	均值	标准差	变异系数/%
TDS	84	2.30×10⁴	656.00	4 376.54	5 289.01	120.85
K⁺	84	149.00	0.59	24.46	37.78	154.46
Na⁺	84	6.98×10³	50.30	1 184.35	1 568.53	132.44
Ca²⁺	84	929.00	18.20	158.20	141.47	89.42
Mg²⁺	84	939.00	7.24	174.91	188.50	107.77
$HCO 3 -$	84	1.89×10³	87.00	688.45	267.73	38.89
Cl^-	84	1.20×10⁴	35.00	1 930.96	2 988.43	154.76
$SO 4 2 -$	84	1.44×10³	33.00	399.99	337.47	84.37
$CO 3 2 -$	84	ND	ND
$NO 3 -$	84	148.00	ND	9.61	19.74	205.36
$NO 2 -$	84	5.57	ND	0.18	0.61	344.54
Mn	84	8.02	ND	0.70	1.32	187.17
Fe	84	2.54	ND	0.19	0.53	271.73
pH值	84	8.73	6.80	7.43	0.34	4.56

Fig.3 Gas station groundwater chemical types in the study area

Fig.4 Spatial distribution of gas station groundwater chemical types in the study area

Table 2 Main factor loadings of groundwater hydrochemical indexes

水化学指标	各主因子载荷
水化学指标	F1	F2	F3	F4
Na⁺	0.98	0.04	0.09	0.06
Cl^-	0.96	-0.02	0.17	0.04
K⁺	0.94	-0.04	-0.17	0.09
Mg²⁺	0.89	0.02	0.31	0.08
Mn	0.80	-0.12	0.02	-0.08
Fe	-0.03	0.90	-0.13	0.02
TPH	-0.36	0.72	0.16	-0.08
$HCO 3 -$	0.17	0.72	-0.09	-0.12
Ca²⁺	0.36	-0.07	0.80	0.11
pH	0.10	0.05	-0.79	0.15
$SO 4 2 -$	0.31	-0.03	0.36	0.34
$NO 3 -$	-0.06	-0.05	0.15	0.82
$NO 2 -$	0.08	-0.10	-0.28	0.73
特征值	4.57	1.88	1.72	1.39
方差贡献率/%	35.16	14.49	13.18	10.72
累积方差贡献率/%	35.16	49.65	62.83	73.55

Table 2 Main factor loadings of groundwater hydrochemical indexes

水化学指标	各主因子载荷
水化学指标	F1	F2	F3	F4
Na⁺	0.98	0.04	0.09	0.06
Cl^-	0.96	-0.02	0.17	0.04
K⁺	0.94	-0.04	-0.17	0.09
Mg²⁺	0.89	0.02	0.31	0.08
Mn	0.80	-0.12	0.02	-0.08
Fe	-0.03	0.90	-0.13	0.02
TPH	-0.36	0.72	0.16	-0.08
$HCO 3 -$	0.17	0.72	-0.09	-0.12
Ca²⁺	0.36	-0.07	0.80	0.11
pH	0.10	0.05	-0.79	0.15
$SO 4 2 -$	0.31	-0.03	0.36	0.34
$NO 3 -$	-0.06	-0.05	0.15	0.82
$NO 2 -$	0.08	-0.10	-0.28	0.73
特征值	4.57	1.88	1.72	1.39
方差贡献率/%	35.16	14.49	13.18	10.72
累积方差贡献率/%	35.16	49.65	62.83	73.55

Table 3 Biodegradation kinetics of TPH in the presence of 4 electron acceptors used in this study

电子受体	生物降解反应		自由能/(kJ·mol^-1)	反应顺序
$NO 3 -$	5CH₂O+4 $N O 3 -$ →2N₂+4 $H C O 3 -$ +CO₂+3H₂O	(3)	-448	1st
Mn⁴⁺	CH₂O+3CO₂+2MnO₂+H₂O→Mn2+4 $H C O 3 -$	(5)	-349	2nd
Fe³⁺	CH₂O+7CO₂+4Fe(OH)₃→Fe2++8 $H C O 3 -$ +3H₂O	(4)	-114	3rd
$SO 4 2 -$	2CH₂O+ $S O 4 2 -$ →H₂S+2 $H C O 3 -$	(6)	-77	4th

Table 3 Biodegradation kinetics of TPH in the presence of 4 electron acceptors used in this study

电子受体	生物降解反应		自由能/(kJ·mol^-1)	反应顺序
$NO 3 -$	5CH₂O+4 $N O 3 -$ →2N₂+4 $H C O 3 -$ +CO₂+3H₂O	(3)	-448	1st
Mn⁴⁺	CH₂O+3CO₂+2MnO₂+H₂O→Mn2+4 $H C O 3 -$	(5)	-349	2nd
Fe³⁺	CH₂O+7CO₂+4Fe(OH)₃→Fe2++8 $H C O 3 -$ +3H₂O	(4)	-114	3rd
$SO 4 2 -$	2CH₂O+ $S O 4 2 -$ →H₂S+2 $H C O 3 -$	(6)	-77	4th

Fig.5 Co-occurrence network diagram of TPH in groundwater of gas stations in the study area

Fig.6 Relationship between TPH and TDS in gas station groundwater in the study area

Fig.7 Relationship between TPH and Mn, SO 4 2 -, NO 3 -, Fe in gas station groundwater

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